Butenol alkanol amines



Patented Feb. 14, 1950 Merton W. Lang, Jr.,'Mia1 1ijIi, llllich.,'assignor to The Dow Chemical Companyflylidland,Michal a corporation of Delawar .Nb Drawing. Application more. 16,1048,

.1... Serial No. 55,020

invention relates to certain new aminoalcohcls containing at least one 3-buten-2-ol radical. 5

The new compounds of the invention-maybe defined as hydroxyaliphatic monoamines having attached to the nitrogen atom thereof a 3-buten- 2-ol radical, a Z-hydroxyalkyl radical containing from two to three carbon atoms, and, as the third substituent, hydrogen or one of the foregoing radicals. They are all stable colorless or yellowish clearliquids of high boiling point. All are sumcanny basic to be titratable to a methyl red endpoint .with normal hydrochloric acid. They areuseful in the manufacture of emulsifying agents, as corrosion inhibitors, and to'some de-- gree\ as stabilizing agents 'for synthetic resins. Bylvirtue of the unsaturated aliphatic radical present, they are 'more readily oxidizable than most alkanolamines and under some conditions exhibit reducing or drying properties.

The new compounds are most conveniently prepa'red'by the reaction of butadiene monoxide (3,4-epoxybutene-1) with an alkanolamine containing one or two 2-hydroxyalkyl radicals per molecule, each such radical having two or three carbon atoms. Depending on the final product desired, the alkanolamine reactant may be either a monoalkanolamine, i. e. monoethanolamine or monoisopropanolamine, or a dialkanolamine; i. e. diethanolamine, diisopropanolamine, or monoethanol monoisopropanolamine (J. Org. Chem. 11,288 (,1946)). v

Inthe reaction of butadiene monoxide with a monalkanolamine; one or two male of the former may be used per mol of the latter, depending upon whether a dior a tri-(hydroxaliphatic) amine is to be prepared. In the reaction with a dialkanolamine, approximately equimolecular proportions of the latter and of butadiene monoxide are used. In general, an excess of butadiene monoxide over the stoichiometric proportion is to be avoided, particularly in making tri-(hydroxyaliphatic) amines, in order to prevent over-reaction with formation of complex ethers.

According to a'preferred procedure for making the new compounds, the butadiene monoxide is added gradually to the alkanolamine in a vessel provided with a reflux condenser and agitator. Since the reaction is slow at ordinary temperatures, the allianolamine is first warmed to 50 to 60 C. Inasmuch as the reaction is highly exothermic, the butadiene monoxide should be added slowly. It may also be desirable to have artificial cooling available since in general the 8 Claims. (01160 5351 v temperaturslhould notexceed 100 c. ifrorma tion of undesirable byproducts is to bea'voide'dl' Temperatures of to 8,5 C. are quitesatis factory.

' Theprocess isbest carried out simply' by mixing' the two reactantsin the absence-of water orother diluents; However, such substances may usually betolerated." 1 l After the appropriate proportion of butadiene monoxide has 1 been added to the alkanolamine, the' mixture is=retained at a reaction temperature until evolution of=-heat tstopsm The resulting material isthen worked up,- usuallyv byrectification at reduced pressure, to separate the" desired product. Y I

The following examples will further illustrate the invention.

' Ezrarriple 1 v A charge of 12.0zgram+m01s of anhydrous monoethanolamine was placed in a reaction vessel provided with an agitator and reflux condenser andfwarmed to approximately 60? C. 'Butadiene monoxide, 7.8 gram-mole. in all, was added slowly over a period of several hours, cooling being applied as j'ne'eded to limit the temperature to below C. Following addition of the butadiene monoxide the mixture was agitated for several hours more to insure completion of the reaction. The crude product, which was a-colorless liquid, had, a. molecular weight of- 99' as determinedby titration This product was separated into its components by rectification in a heated column at anabsolutepressure of 1.0 mm.,-'of mercury, and was thus found to contain 24.4% unreacte'd monoethanolamine, 56.6% monoethanol mono- 3-buten- 2-ol-amine 18.3% monoethanol di-3- buten-Z-Ol-amine, and 0.7% high boiling residue. The purified monoethanclmono-3-buten-2-ol amine (1'-(2-hydroxyethylamino) -3-buten-2-ol) "(C6H13NO2); was a colorless'liquid having a specific gravity of 1.054 at 25/25*C. and a refractive 'index'of'1.4860' n Its vapor pressure at 125.5 C. was 2.5 mm. of mercury absolute and at 2 '05.5TC.was,123 .4 mm. 4 Example 2 Following the general procedure of Example 1, 15.2 gram-mols of butadiene monoxide was added slowly to 8.0 gram-mols of anhydrous monoethanolamine maintained at 60 to 85 C. The crude product had a molecular weight by analysis of 197. On fractional distillation at a pressure below 1.0 mm. of mercury absolute, the product was found to contain 86.5% by weight of mono- 3 ethanol di-3-buten-2-ol-amine,(1,1- (Z-hydroxyethylimino) -di-3-buten-2-ol) (C10H19NO3) This purified material had a specific gravity of 1.060 at 25/25 C. and a refractive index of 1.4946 11 Its vapor pressure at 160.0 C. was 1.0 mm. of mercury absolute and at 225.1 C. was

Example 3 1.088 at 25/25 C. and a refractive index of' 1.4900 n Its vapor pressure at 160.8 C. was 1.0mm. of mercury absolute and at 239.4 C.'was 4916mm,

Earample 4 To a charge of 12.0 gram-mols of anhydrous mono-isopropanolamine, 7.8 gram-mols of buta diene monoxide was added slowly according to the procedure of Example 1. The molecular weight of the crude product was 120. On fractional distillation at an absolute pressure below 1.0 mm.

of mercury, the product was found to contain 51.6% of mono-isopropanol-mono-3butch-2e01- amine, (1- (2-hydroxypropylamino) -3-buten-2-0l) (C'1H15NO2).

The purified material had a specific gravity of 1.016 at 25/25 C. and a refractive index' of 1.4770 11 The vapor pressure at 115.5? C. was 2.5 mm. of mercury absolute and at 207.0 C. was 154.3 mm.

Example 5 To a charge of 7 gram-mols of' anhydrous :mono-isopropanolamine, 14.6 gram molsof buta- -diene monoxide was added according tothe procedure of Example 1. The molecular weight of thecrude product was 229. On fractional distillation at an absolute pressurebelow 1.0 min. or mercury, the product was found 'to contain 86.3% of monoisopropanol di-3-buten-2-olamine, 1,1 (2-hydroxypropylimino)'-di-3 buten'- 20l1)"(C11I-I21NO3 I v A U The purified material had a specific gravity of 1.033 at /25" C. and a refractive index" of 1.4870 11 The vapor pressure at 165.5? C. was 3.0 of mercury absolute and at:245.0 C; was 116.4 mm.

' Example 6 To a charge of 8 gram-mols of anhydrous diiso propanolamine, 7.2 gram-mols of butadiene monoxidewas added according to the' procedure of Example 1. The molecular weight of the crude product was 196. On fractional distillation at an absolute pressure below 1.0 mmofimercury, the product was found to contain 90.0% of diiso'priopanol mono-3-buten-2-ol amine, (1-( bis(2-hydroxyethyl) -amino) -3-buten-2-ol) (Ci'oH'z'iNOz).

The crude producthad a molec The purified material had a specific gravity of 1.027 at 25/25" C. and a refractive index of 1.4771 11 The vapor pressure at 147.4 C. was 1.0 mm. of mercury absolute and at 237.1 C. was 93.8 mm.

Ealample 7 To a charge of 7 mol-grams of anhydrous monoethanol mdnoisopro panolaniine," 6.65 grammols of butadiene monoxide was added according to the procedure of Example 1. The molecular weight of the crude product was 189. On fractional distillation at an absolute pressure below 1.0 mm; 'of mercury, the product was found to contain 94.4% of monoethanol monoisopropanol mono-'3-buten-2-ol-amine, (1-N-(2-hydroxyethyl) -N- (2-hydroxypropyl) amino-3-buten-2-ol) (C9H19NO3) The purified material had a specific gravity of 1.053 at 25/25- C. and a refractive index of 1.4816 n The vapor pressure at 149.0" C. was 1.0 mm; of mercury absolute and'at 247.0 C. was 100.6 mm.

What is claimed is: a v v e 1.- A hydroxyaliphatic monoamine having attached to the nitrogen atom thereof asithe sole organic substituents thereon not more than thre e radicals consisting of from one to'two-3-but'en- 2-01 radicals and from one to two 2 hydroxy'a1kyl radicals each containing from two to three carbon atoms. I V v 2. A'compound according to claim 1 containing one 3-buten-2-ol radical. I

3. A compound according to claiml containing two 3-buten-2-ol radicals. I

4. Diethanol mono-3-buten-2-ohamine; a'liq uid having a boiling point of about 161 C. at 1.0 mm. of mercury absolute pressure and aspecific gravity of about 1.088.

5. Diisopropanol mono-3-buten-2-ol-amine', a liquid having a boiling'point of about 147? C. at

-- 1.0 mm. of mercury absolutepress'ure and a spe- REFERENCESCITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name a v Date 2,119,802 Westphal et a1 June 7 1938 2,198,260 Van Melson Apr. 23,1940 2,404,691 Christainsen et al. 'July 23, 1946 

1. A HYDROXYALIPHATIC MONOAMINE HAVING ATTACHED TO THE NITROGEN ATOM THEREOF AS THE SOLE ORGANIC SUBSTITUENTS THEREON NOT MORE THAN THREE RADICALS CONSISTING OF FROM ONE TO TWO 3-BUTEN2-OL RADICALS AND FROM ONE TO TWO 2-HYDROXYALKYL RADICALS EACH CONTAINING FROM TWO TO THREE CARBON ATOMS. 